Studies in laboratory animals and tissues and cells in vitro have shown that the formation of carcinogen-DNA adducts is necessary but not sufficient for chemical carcinogenesis. Following environmental exposure, it seems reasonable that these types of adducts are formed in humans. Since the biologically effective dose of a chemical carcinogen is governed by the amount of carcinogen that becomes internalized and activated to a chemical species capable of damaging DNA, it seems reasonable to develop methods to detect these adducts. Human carcinogen dosimetry at the molecular level requires sensitive and specific methods for carcinogenmacromolecular adduct quantitation. A number of different types of methods have been developed for carcinogen-DNA dosimetry in humans. These include the 32P-nucleotide postlabeling assay, immunoassays, fluorescence spectroscopy, electrochemical conductance and gas chromatography/mass spectroscopy (GC/MS). Each technique has advantages and limitations, and within the framework of epidemiological surveys multiple corroborative end-point analyses often provide the most useful information. Our studies are focused on the use of separatory techniques to achieve chemical specificity prior to sensitive detection by different corroborative methods.